Acetal polymers and use thereof in photosensitive compositions and lithographic printing plates

ABSTRACT

This invention relates to a binder containing the units A, B, C, D and E, wherein A is present in an amount of 10 to 60 mole % and is of the formula ##STR1## B is present in an amount of 1 to 30 mole % and is of the formula ##STR2## C is present in an amount of 5 to 60 mole % and is of the formula ##STR3## D is present in an amount of 0 to 60 mole % and is of the formula ##STR4## and E is present in an amount of 1 to 40 mole % and is of the formula ##STR5## wherein X is an aliphatic, aromatic or araliphatic spacer group, 
     R 1  is hydrogen or an aliphatic, aromatic or araliphatic group, 
     R 2 , R 3  and R 4  are hydrogen or alkyl groups with carbon numbers of from 1 to 18 and 
     Y is a saturated or unsaturated chain- or ring-shaped spacer group, and photosensitive compositions containing this binder.

This application is a division of application Ser. No. 08/675,024, filedJul. 3, 1996 now U.S. Pat. No. 5,700,619.

The present invention relates to binders and photosensitive compositionscomprising said binders and inter alia excellently suitable for theproduction of lithographic plates.

Nowadays, photosensitive compositions usable particularly forhigh-performance lithographic plates must fulfill high requirements.

The discussion of improving the properties of photosensitivecompositions and thus also of the corresponding lithographic platesessentially deals with two different ways. One of them deals with theimprovement of the properties of the photosensitive components in thecompositions (frequently diazo resins, photo polymers etc.), the otherone with the search for novel polymeric compounds ("binders") which areto control the physical properties of the photosensitive layers. Inparticular the latter way is decisive for lithographic plates becausethe behavior in the developing and printing processes (such asdevelopability, ink receptivity, scratch resistance, consistency in thenumber of prints produced) is decisively influenced by the polymericbinders. Also shelf life and photosensitivity of the materials arestrongly influenced by the polymeric compounds.

The polymeric binders therefore exhibit various structural elements forsatisfying the extensive requirements, which may have different effectson individual properties. For instance, hydrophilic structural elementssuch as carboxyl groups, hydroxyl groups and the like generally promotethe developability of the photosensitive compositions in aqueousalkaline developers and partly ensure sufficient adhesion to polarsubstrates. Hydrophobic structural elements, on the other hand, reducethe capability of being developed in the above-mentioned developers, butensure the good ink receptivity used in the printing process, which isindispensable in lithographic plates.

Due to the broad range of requirements regarding the polymeric binders,for many years there have been extensive studies on the synthesis andoptimization of these substances for photosensitive compositions, cf.e.g. H. Baumann and H.-J. Timpe: "Chemical Aspects of Offset Printing"in J. prakt. Chem./Chemiker-Zeitung [Journal for chemists] 336 (1994)pages 377-389.

EP-A-135 026, EP-A-186 156 and U.S. Pat. No. 4,731,316 describe bindersystems consisting of compositions of polymers having differenthydrophilic/hydrophobic properties. However, such compositions involvethe disadvantage that very frequently incompatibilities between thedifferent substances lead to separation during the formation of layers.Furthermore, it was found that the hydrophobic polymers precipitateduring the developing process, which may lead to silting in thedeveloping machines.

Furthermore, copolymers consisting of only slightly hydrophilic monomerssuch as styrene, acrylic acid ester, methacrylic acid ester and the likewith hydrophilic comonomers were described. Examples of such comonomersare semi-esters of maleic acid (DE-A-31 30 987, EP-B-71 881, EP-A-104863), itaconic acid (EP-A1-397 375, U.S. Pat. No. 5,260,161) and acrylicacid and/or methacrylic acid (EP-A-487 343, U.S. Pat. No. 4,304,832,U.S. Pat. No. 4,123,276). The very tight play of the propertiesimportant for the use, which are layer adhesion, developability andprinting ink receptivity proved to be disadvantageous in such polymers.Variations in the polymers' composition can hardly be avoided during theproduction process, which leads to unacceptable fluctuations in theplates' properties.

DE-A-27 51 060 describes photosensitive compositions, wherein the binderis a reaction product of cellulose esters with cyclic, intermolecularacid anhydrides of dicarboxylic acids. These binders, however, are notoleophilic enough for the use in lithographic plates formulations.

Polymers that contain urethane groups were also described as binders forphotosensitive compositions (EP-A2-415 302, EP-A1-406 599, EP-A1-406600, EP-A2-414 099, U.S. Pat. No. 4,983,491, U.S. Pat. No. 4,950,582,U.S. Pat. No. 4,877,711). The necessary functionalization with suchhydrophilic groups, however, requires very high efforts regardingsynthesis and involves high costs.

Extensive studies have been carried out on polyvinyl acetals as bindersfor photosensitive compositions. In order to achieve sufficientdevelopability in the case of a use in offset printing molds, variousdirections have been taken.

If, as described in EP-B1-216 083, only pure aliphatic aldehydes areused for the acetalization of the polyvinyl alcohols, depending on thedegree of reaction the result are either poorly adhesive layers ormixtures with too low a developability.

Although, the relation between adhesion and developability is improvedin the acetalization with purely aliphatic aldehydes in combination withOH groups containing aliphatic aldehydes claimed in EP-B1-274 075, thepractical requirements cannot be met yet. To improve developability, inDE-20 53 363, DE-20 53 364 and EP-B1-48 876 sulfonyl urethane groupswere introduced into polyvinyl acetals. The low acidity of these groups,however, makes developers necessary that contain a high portion ofsolvents. In addition, micro-elements of such prepared lithographicplates exhibit very low adhesion so that wear takes place rapidly duringthe printing process.

GB-1 396 355 describes binders that may be prepared by acetalization ofsaponified copolymers from vinyl acetate and a carboxyl group bearingmonomer such as crotonic acid. This kind of binders, however, leads tosystems with low photosensitivity and little consistency in the numberof prints produced when used for lithographic molds. EP-B1-211 391 andEP-B1-152 819 introduce the carboxyl groups by reaction of separatelyprepared acetals of aliphatic aldehydes with polyvinyl alcohol withintermolecular, cyclic acid anhydrides of dicarboxylic acids. Theefforts necessary for synthesis, however, are extensive since thereaction with the acid anhydrides, which is only possible in aproticsolvents, must take place in addition to the acetalization. Furthermore,the photosensitivity of the mixtures produced from these binders isstill too low. EP-B1-208 145 describes binders produced in a three-stepsynthesis starting from polyvinyl alcohol: acetalization with aliphaticaldehydes, reaction with intermolecular, cyclic acid anhydrides ofdicarboxylic acids and partial esterification of the carboxyl groupswith substituted alkyl halides. Despite the extensive effort requiredfor the binder synthesis, improved photosensitivity of the coatingsprepared therefrom is still desirable. The effort of the multi-stepsynthesis may be avoided if, as described in PCT-WO-93/03068, U.S. Pat.No. 4,652,604, U.S. Pat. No. 4,895,788, U.S. Pat. No. 4,940,646 and U.S.Pat. No. 5,169,897, polyvinyl alcohol is reacted with aliphaticaldehydes and carboxyl groups containing aromatic aldehydes. Thephotosensitive compositions produced therefrom, however, have anundesired relationship between developability and sensitivity.

Despite this intensive research carried out in the field ofphotosensitive compositions for lithographic plates, all existingcompositions make improvement appear desirable, in particular regardingtheir sensitivity, developability and the number of prints produced.Furthermore, many of the compositions exhibit a high number of partiallyrather expensive components, which make an economical use impossible.

It is thus the object of this invention to provide binders andphotosensitive compositions comprising said binders and doing with asfew components as possible vis-a-vis the compositions described in thestate of the art (which makes them economically desirable) and stillhaving the same or--in individual areas--improved physical properties.In particular, an improved photosensitivity, improved printing inkreceptivity and/or an increased number of prints produced from thecorresponding lithographic plates vis-a-vis the compositions describedin the state of the art are to be achieved.

Another object underlying this invention is the use of suchphotosensitive compositions for preparing lithographic plates.

These objects are achieved by a photosensitive composition comprising:

(i) a diazonium polycondensation product or a free radical polymerizablesystem consisting of photoinitiators and unsaturated compounds which arefree radical polymerizable or a hybrid system consisting of a diazoniumpolycondensation product and a free radical polymerizable systemconsisting of photoinitiators and unsaturated compounds which are freeradical polymerizable,

(ii) a binder and optionally one or more exposure indicator(s), one ormore dye(s) for increasing the contrast of the image as well as one ormore acid(s) for stabilizing the photosensitive composition,characterized in that the binder consists of units A, B, C, D and E,wherein A is present in an amount of 10 to 60 mole % and is of theformula ##STR6## B is present in an amount of 1 to 30 mole % and is ofthe formula ##STR7## C is present in an amount of 5 to 60 mole % and isof the formula ##STR8## D is present in an amount of 0 to 60 mole % andis of the formula ##STR9## and E is present in an amount of 1 to 40 mole% and is of the formula ##STR10## wherein X is an aliphatic, aromatic oraraliphatic spacer group,

R¹ is hydrogen or an aliphatic, aromatic or araliphatic moiety

R², R³ and R⁴ are hydrogen or alkyl groups with carbon numbers of from 1to 18 and

Y is a saturated or unsaturated chain- or ring-shaped spacer group.

The surprising advantages of the invention are that by means of a rathersimple synthesis and starting from inexpensive polymers available inlarge-scale technology, specific polymers can be prepared. A widevariety of properties of the thus obtained polymer can be exactlyadjusted due to the multitude of possibilities offered by the method ofthis invention regarding kind and amount of the carboxyl group bearingmoiety HOOC--Y--CO--NR¹ --X--CH(O--)₂, the choice of hydrophobicsubstituents R³ and R⁴, the amount of esterified OH groups as well asthe choice of molecular weight of the polymer to be modified. This way,tailor-made polymers can be obtained suitable for variousphoto-crosslink mechanisms.

Besides, it was found that the obtained photosensitivities and thechemical and mechanical properties of the photosensitive compositionscan be considerably improved, in particular for the use in offsetlithographic plates.

The first essential component of the photosensitive composition of thisinvention is a polyvinyl alcohol, the OH groups of which are acetalizedwith different moieties.

The polyvinyl alcohols preferably used for the synthesis have a residualcontent of esterified groups in the range of from 0.3 to 30 wt. %. Morepreferred are polyvinyl alcohols prepared starting from polyvinylacetate, i.e. R² =CH₃ with a residual acetate content of from 1.5 to 22wt. %. The behavior in alkaline developers and the photosensitivity ofthe photosensitive compositions produced can be influenced by themolecular weight of the polyvinyl alcohols used in the synthesis.Preferably used polyvinyl alcohols exhibit viscosities of between 2 and26 mPa.s as 4% aqueous solution in water at 20° C.

The acetalization of the polyvinyl alcohols takes place according toknown standard methods; examples are described in EP-B-216 083 andDE-A-28 38 025.

The acetal moieties can be represented starting from aldehydes R³ CHO,R⁴ CHO and HOOC--Y--CO--NR¹ --X--CHO or acetals of these aldehydes R³CH(OR⁹)₂, R⁴ CH(OR⁹)₂, or HOOC--Y--CO--NR¹ --X--CH(OR⁹)₂, wherein R⁹ isalkyl. This reaction generally requires the addition of a stronginorganic or organic catalyst acid. Examples of catalyst acids arehydrochloric acid, sulfuric acid, phosphoric acid or p-toluenesulfonicacid. A particularly preferred catalyst acid is hydrochloric acid. Theamount of acid added should preferably be 1 to 25 wt. % based on theamount of polyvinyl alcohol used.

The reaction temperature of the acetalizations depends on the kind ofaldehyde as well as the desired amount of reaction. It is between 0° C.and, if applicable, the boiling point of the used solvent. Preferablythe temperatures are between 5° C. and 100° C.

Organic solvents as well as mixtures of water with organic solvents areused as acetalization agents. Particularly suitable organic solvents arealcohols (such as methanol, ethanol, propanol, butanol or glycol ether),cyclic ethers (such as tetrahydrofuran, 1,4,-dioxane, 1,3-dioxolane) ordipolar aprotic solvents (such as dimethyl sulfoxide, formamide,N,N-dimethyl formamide, hexamethyl phosphoric acid triamide or N-methylpyrrolidone). If the acetalization is carried out in organic solvents ormixtures of organic solvents with water, the reaction product oftenremains in solution even if the starting polyvinyl alcohol was notcompletely dissolved. This offers the advantage that the degree ofreaction is relatively easy to reproduce. The sequence of the additionof the various acetalization agents is often of no importance andcomparable finished products are obtained from different preparationsequences. To isolate the finished product as a solid, the polymersolution is introduced into a non-solvent under stirring, filtered offand dried. Water is especially suitable as non- solvent for the polymer.Another, also practicable method is to add the non-solvent for thepolymer under stirring to the synthesis solution. In this method too,water is a preferred non-solvent.

For obtaining certain properties of the polymeric binder, it may beadvantageous to isolate the polymer between individual acetalizationsteps by means of precipitation, and to continue the acetalization upondissolution in an optionally different solvent than that of the previousacetalization step.

The moieties R³ and R⁴ are hydrogen or branched or straight-chain alkylgroups having preferably 1 to 18 carbons, more preferably 1 to 6carbons. Particularly preferred is the synthesis starting fromacetaldehyde, propionaldehyde and butyraldehyde and/or their acetals oflow alcohols R⁹ OH.

The carboxyl group bearing acetal is readily introduced under the aboveconditions starting from aldehydes HOOC--Y--CO--NR¹ --X--CHO or acetalsof these aldehydes HOOC--Y--CO--NR¹ --X--CH(OR⁹)₂. The preparation ofthe aldehydes or acetals necessary for the polymer synthesis is alsoeasily possible starting from the corresponding amine NHR¹ --X--CH(OR⁹)₂by reaction with an intermolecular, cyclic carboxylic acid anhydride offormula I. ##STR11##

The reaction takes place quantitatively at room temperature in aproticsolvents. Preferred solvents are benzene, toluene, xylene,tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and the like. When anappropriate solvent is chosen, it can be achieved that the final productis insoluble in the solvent and precipitates. Appropriate solvents forthis are non-polar solvents such as hexane, cyclohexane and the like.Another variant is to prepare HOOC--Y--CO--NR¹ --X--CH(OR⁹)₂ in thesolvent suitable for the reaction to form the polymer and to thus avoidhaving to isolate it as a free substance. Particularly suitable solventsfor this are cyclic ethers (such as tetrahydrofuran, 1,4-dioxane,1,3-dioxolane) or dipolar aprotic solvents (such as dimethyl sulfoxide,formamide, N,N-dimethyl formamide, hexamethyl phosphoric acid triamideor N-methyl pyrrolidone). Under certain conditions it may beadvantageous to use the free aldehyde HOOC--Y--CO--NR¹ --X--CHO whenintroducing the carboxyl group bearing acetal group. It is easilyaccessible by means of a mild hydrolysis from the above-describedacetal.

The amine NHR¹ --X--CH(OR⁹)₂ used for the reaction with theintermolecular, cyclic carboxylic acid anhydride of formula I maycomprise a hydrogen, a branched or straight-chain alkyl, an aryl oraralkyl as substituent R¹, preferably hydrogen and alkyl. A morepreferred moiety R¹ is hydrogen or a methyl group. The spacer group Xmay be of aliphatic, aromatic or araliphatic nature. Preferably usedspacer groups are --CH₂ --, --CH(CH₃)-- or --CH₂ CH₂ CH₂ --.

The following compounds are suitable intermolecular, cyclic carboxylicacid anhydrides of formula I:

maleic anhydride and derivatives thereof (such as dimethyl maleicanhydride or citraconic anhydride),

phthalic acid anhydride and its substitution products (such as chloro-,nitro- and carboxyphthalic acid anhydride) and hydrogenation products(such as tetrahydrophthalic acid anhydride),

succinic anhydride and derivatives thereof (such as methyl succinicanhydride),

glutaric anhydride and derivatives thereof (such as 3-oxaglutaricanhydride, 3-methylglutaric anhydride, 3,3-tetramethylene glutaricanhydride or camphoric anhydride),

naphthalenedicarboxylic acid anhydride and its substitution products(such as naphthalene-2,3-dicarboxylic acid anhydride andnaphthalene-1,8-dicarboxylic acid),

pyridine-o-carboxylic acid anhydride and its substitution products,

pyrazine-o-carboxylic acid anhydride and its substitution products,

o-furancarboxylic acid anhydride and its substitution products,

thiophene-o-carboxylic acid anhydride and thiophene-2,5-dicarboxylicanhydride, the substitution products thereof as well as the completelyor partially hydrogenated derivatives thereof and

di- or polycyclic anhydrides resulting from Diels-Alder reaction of adiene with maleic anhydride (such as addition products from furan,anthracene, cyclohexadiene-1,3, or cyclopentadiene and maleicanhydride).

More preferred are maleic, phthalic acid, tetrahydrophthalic acid,succinic and 3-oxaglutaric acid anhydride

The spacer group Y is preferably

--CR⁵ R⁶ --CR⁷ R⁸ --, --CR⁵ ═CR⁶ --, ##STR12## wherein R⁵, R⁶, R⁷, R⁸independently are hydrogen or alkyl.

The right composition of the polymer of this invention requiresoptimization tests for the individual desired application.Developability, photosensitivity, printing ink receptivity, shelf-lifeunder elevated humidity and temperature etc. dependent on thecomposition of the polymer are determined in a manner known to theperson skilled in the art.

The second substantial component of the photosensitive mixture of thisinvention is a diazonium polycondensation product or a free radicalpolymerizable system, consisting of photoinitiators and unsaturatedcompounds, which are free radical polymerizable, or a hybrid systemcomprising a diazonium polycondensation product and a free radicalpolymerizable system comprising photoinitiators and unsaturatedcompounds which are free radical polymerizable.

In the photosensitive mixtures according to the invention, diazoniumpolycondensation products known to the person skilled in the art can beused as diazonium polycondensation product. Such condensation productsmay for instance be prepared in a common manner by condensation of adiazo monomer described in EP-A-0 104 863 with a condensation agent,such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,isobutyraldehyde or benzaldehyde. Furthermore, mixed condensationproducts are used which, apart from the diazonium salt units, compriseother non-photosensitive units which are derived from condensablecompounds, in particular from aromatic amines, phenols, phenol ethers,aromatic thioethers, aromatic hydrocarbons, aromatic heterocycles ororganic acid amides. Especially advantageous examples of diazoniumpolycondensation products are reaction products ofdiphenylamine-4-diazonium salts, optionally having a methoxy group inthe phenyl group bearing the diazo group, with formaldehyde or4,4'-bis-methoxymethyl diphenyl ether. Aromatic sulfonates such as4-tolylsulfonate or mesitylene sulfonate, tetrafluoroborate,hexafluoro-phosphate, hexafluoroantimonate and hexafluoroaresenate areparticularly suitable as anions of these diazo resins. The diazoniumpolycondensation product is preferably present in the photosensitivemixtures in an amount of from 3 to 60 wt. %.

The second substantial component may also be a free radicalpolymerizable system. This is made up of photoinitiators absorbing inthe range of from 300 to 800 nm, preferably 300 to 450 nm, and freeradical polymerizable components. The basic bodies and/or derivatives ofacetophenone, benzophenone, (trichloromethyl)-1,3,5-triazine, benzoine,benzoine ethers, benzoine ketales, xanthone, thioxanthone, acridine orhexaryl-bis-imidazole are preferred photoinitiators for thephotosensitive compositions of this invention. The free radicalpolymerizable component of the mixture of this invention is an acrylicor methacrylic acid derivative having one or more unsaturated group(s),preferably esters of acrylic or methacrylic acid in the form ofmonomers, oligomers or prepolymers. It may be present in solid or liquidform, solid and highly viscous forms being preferred. The compoundssuitable as monomers include for instance trimethylol propanetriacrylate and methacrylate, pentaerythritol triacrylate andmethacrylate, dipentaerythrite-monohydroxy pentaacrylate andmethacrylate, dipenta erythritolhexaacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, di(trimethylolpropane)tetraacrylate and methacrylate, diethylene glycol diacrylate andmethacrylate, triethylene glycol diacrylate and methacrylate ortetraethylene glycol diacrylate and methacrylate. Suitable oligomersand/or prepolymers are urethane acrylate and methacrylate, epoxideacrylate and methacrylate, polyester acrylate and methacrylate,polyether acrylate and methacrylate or unsaturated polyester resins. Thephotoinitiators and free radical polymerizable components are to bearranged in a manner known to the person skilled in the art,combinations of various photoinitiators and different free radicalpolymerizable components being also advantageous. The weight ratio ofthe photoinitiators is preferably 0.5 to 20% and that of the freeradical polymerizable components 5 to 80%, based on the total solidcontent of photosensitive compositions.

A combination of the diazonium polycondensation products having a freeradical polymerizable system comprising photoinitiators and unsaturatedcompounds, which are free radical polymerizable, may be advantageous forcertain applications. The compositions of such hybrid systems preferablycomprise 1 to 50% diazonium polycondensation products, 0.5 to 20%photoinitiators as well as 5 to 80% free radical polymerizablecomponents.

The exposure indicators usable in the photosensitive mixtures of thisinvention are known to the person skilled in the art. Exposureindicators from the group of triaryl methane dyes (such as Victoria blueBO, Victoria blue R, Crystal Violet) or azo dyes (such as4-phenyl-azo-diphenylamine, azobenzene or4-N,N-dimethyl-amino-azo-benzene) are preferred. The exposure indicatorsare present in the photosensitive mixture at a ratio of 0.02 to 10 wt.%, preferably 0.5 to 6 wt. %.

Suitable dyes for improving the contrast of the image are those thatdissolve well in the solvent or solvent mixture used for coating or areeasily introduced in the disperse form of a pigment. Suitable contrastdyes include inter alia rhodamin dyes, methyl violet, anthrachinonepigments and phthalocyanine dyes and/or pigments.

Furthermore, the mixture of this invention may comprise stabilizingacids. These stabilizing acids include phosphoric, citric, benzoic,m-nitrobenzoic, p-anilino azobenzene sulfonic, p-toluene sulfonic ortartaric acid. In some formulations a mixture of several different acidsis advantageous. Phosphoric acid is preferably used as stabilizing acid.The added acid preferably amounts to 0.2 to 6 wt. %.

The photosensitive mixture of this invention may also comprise asoftening agent. Suitable softening agents include dibutyl phthalate,triaryl phosphate and dioctyl phthalate. Dioctyl phthalate is especiallypreferred. The amount of softening agent used is preferably 0.25 to 2wt. %.

The photosensitive mixtures of this invention are preferably usable forproducing lithographic plates. In addition, however, they may be used inrecording materials for creating images on suitable carriers andreceiving sheets, for creating reliefs that may serve as printing molds,screens and the like, as light-hardening varnishes for surfaceprotection and for the formulation of UV-hardening printing inks.

For the preparation of planographic printing plates aluminum as thecarrier is first roughened by brushing in a dry state, brushing withabrasive suspensions or electrochemically, e.g. in an hydrochloric acidelectrolyte.

The roughened plates, which were optionally anodically oxidized insulfuric or phosphoric acid, are then subjected to a hydrophilizingaftertreatment, preferably in an aqueous solution of polyvinylphosphonic acid, sodium silicate or phosphoric acid. The details of theabove-mentioned substrate pretreatment are well-known to the personskilled in the art.

The dried plates are then coated with the photosensitive layers oforganic solvents and/or solvent mixtures so that dry layer weights ofpreferably from 0.5 to 4 g/m², more preferably 0.8 to 3 g/m², areobtained.

In some cases the additional application of an oxygen-impermeable toplayer to the photosensitive layer might be advantageous. This isespecially advantageous in free radical polymerizable systems and in thehybrid systems of diazonium polycondensation products and free radicalpolymerizable systems. The polymers suitable for the top layer includepolyvinyl alcohol, polyvinyl alcohol/polyvinyl acetate copolymers,polyvinyl pyrrolidone, polyvinyl pyrrolidone/polyvinyl acetatecopolymers, polyvinyl methyl ether, polyacrylic acid and gelatine. Thethickness of the oxygen-impermeable top layer is preferably 0.1 to 4g/m², and more preferably 0.3 to 2 g/m².

The thus obtained lithographic plates are exposed and developed ascommon and known to the person skilled in the art. The developed platesare usually treated with a preservative ("rubber coating"). Thepreservatives are aqueous solutions of hydrophilic polymers, wettingagents and other additives.

For certain uses it is furthermore advantageous to increase themechanical strength of the printing layers by means of a heat treatmentor a combined use of heat and UV radiation. For this purpose, the plateis first treated with a solution that protects the non-image areas suchthat the heat treatment will cause no ink receptivity in these areas. Asuitable solution is described e.g. in U.S. Pat. No. 4,355,096.

The following examples serve to provide a more detailed explanation ofthe invention.

Preparation Example 1

301.5 g maleic anhydride are dissolved in 750 ml dried tetrahydrofuran.3 60.6 g 2-(N-methylamino)-acetaldehyde dimethyl acetal are addeddrop-wise to this solution while cooled such that the temperature doesnot rise any higher than 20° C. Subsequently, the mixture is refluxedfor 30 minutes and the solvent is distilled off by means of a vacuumrotation vaporizer. The obtained product is oily and crystallizes aftera certain time. The yield is quantitative. The acid number is 253 mg KOHper gram substance.

Preparation Example 2

104 g phthalic acid anhydride are dissolved in 550 ml driedtetrahydrofuran. For better dissolution the mixture is briefly heated toboiling and then cooled to 15° C. In the course of 30 minutes, 79 g2-(N-methylamino)-acetaldehyde dimethyl acetal are added drop-wise tothis solution while cooled such that the temperature does not rise anyhigher than 20° C. Subsequently, the mixture is refluxed for 30 minutesand the solvent is separated by means of a vacuum rotation vaporizer.The yield is quantitative. The acid number is 196 mg KOH per gramsubstance.

Preparation Example 3

96 g tetrahydrophthalic acid anhydride are added to 450 ml driedtetrahydrofuran. For better dissolution the mixture is briefly heated toboiling and then cooled to 15° C. In the course of 30 minutes, 71.4 g2-(N-methylamino)-acetaldehyde dimethyl acetal are added drop-wise tothis solution while cooled such that the temperature does not rise anyhigher than 20° C. Subsequently, the mixture is refluxed for 30 minutesand the solvent is separated by means of a vacuum rotation vaporizer.The yield is quantitative. The acid number is 199 mg KOH per gramsubstance.

Preparation Example 4

75 g Mowiol 8/88® (polyvinyl alcohol available from Hoechst having acontent of residual acetyl groups of approx. 21 wt. %) are dissolved in225 ml water and 450 ml n-propanol at 70° C. in a three-necked flaskequipped with cooler, stirrer and thermometer on a water bath. Thesolution is cooled to 60° C. and 10.2 ml concentrated hydrochloric acidare added. Subsequently, a mixture of 16.2 g butyraldehyde and 9.9 gacetaldehyde is added drop-wise and the mixture is stirred for 4 hoursat 60° C. For neutralization, 10.6 g sodium carbonate dissolved in 50 mlwater are added and the mixture is stirred for 30 minutes. Then, thepolymer is precipitated by slowly pouring the mixture into an excess ofwater, it is filtered off and dried for 24 hours at 40° C. in a rotarydrying chamber. The analytical examination of the product shows 28 wt. %vinyl alcohol units.

Preparation Example 5

100 g of the polymer of Preparation Example 4 are dissolved in 1,500 mldimethyl sulfoxide under stirring. Upon addition of 10 g concentratedhydrochloric acid and 43.4 g of the reaction product of maleic anhydridewith 2-(N-methylamino)-acetaldehyde dimethyl acetal of PreparationExample 1 is stirred at approx. 60° C. for 24 hours. The polymericbinder is precipitated in an excess of water and dried for 24 hours at40° C. in a rotary drying chamber. The analytical examination of theproduct reveals an acid number of 21 mg KOH per gram polymer.

Preparation Example 6

25 g Mowiol 8/88® so (polyvinyl alcohol available from Hoechst having acontent of residual acetyl groups of approx. 21 wt. %) are dissolved in500 ml dimethyl sulfoxide at 70° C. Upon cooling down to 50° C., 2.5 gconcentrated hydrochloric acid and, subsequently, a mixture of 2.64 gacetaldehyde and 4.32 g butyraldeyde in 20 ml dimethyl sulfoxide areadded drop-wise under stirring. After a reaction time of 5 hours, 10.85g of the reaction product from maleic anhydride with2-(N-methylamino)-acetaldehyde dimethyl acetal of Preparation Example 1,dissolved in 30 ml dimethyl sulfoxide are added and stirred for 16 hoursat 60° C. The polymeric binder is precipitated in an excess of water anddried for 24 hours at 40° C. in a rotary drying chamber. The analyticalexamination of the product reveals an acid number of 17 mg KOH per grampolymer.

Preparation Example 7

100 g of the polymer of Preparation Example 4 are dissolved in 785 mldimethyl sulfoxide under stirring. Upon addition of 5.24 g concentratedhydrochloric acid and 53.8 g of the reaction product of phthalic acidanhydride with 2-(N-methylamino)-acetaldehyde dimethyl acetal ofPreparation Example 2, the mixture is stirred for 24 hours at approx.60° C. The polymeric binder is precipitated in 13 l water containing 5.2g soda and dried for 24 hours at 40° C. in a rotary drying chamber. Theanalytical examination of the product reveals an acid number of 15 mgKOH per gram polymer.

Preparation Example 8

100 g of the polymer of Preparation Example 4 are dissolved in 785 mldimethyl sulfoxide under stirring. Upon addition of 5.24 g concentratedhydrochloric acid and 53.8 g of the reaction product oftetrahydrophthalic acid anhydride with 2-(N-methylamino)-acetaldehydedimethyl acetal of Preparation Example 3, the mixture is stirred for 24hours at approx. 60° C. The polymeric binder is precipitated in 13 lwater containing 5.2 g soda and dried for 24 hours at 40° C. in a rotarydrying chamber. The analytical examination of the product reveals anacid number of 36 mg KOH per gram polymer.

Preparation Example 9

100 g of the polymer of Preparation Example 4 are dissolved in 1,500 ml1,4-dioxane under stirring. Upon addition of 10 g concentratedhydrochloric acid and 43.4 g of the reaction product of maleic anhydridewith 2-(N-methylamino)-acetaldehyde dimethyl acetal of PreparationExample 1, the mixture is stirred for 24 hours at approx. 60° C. Thepolymeric binder is precipitated in an excess of water and dried for 24hours at 40° C. in a rotary drying chamber. The analytical examinationof the product reveals an acid number of 18 mg KOH per gram polymer.

Preparation Example 10

100 g of the polymer of Preparation Example 4 are dissolved in 1,000 mltetrahydrofuran under stirring. Upon addition of 10 g concentratedhydrochloric acid and 43.4 g of the reaction product of maleic anhydridewith 2-(N-methylamino)-acetaldehyde dimethyl acetal of PreparationExample 1, the mixture is stirred for 4 hours at approx. 60° C. Thepolymeric binder is precipitated in an excess of water and dried for 24hours at 40° C. in a rotary drying chamber. The analytical examinationof the product reveals an acid number of 8 mg KOH per gram polymer.

Preparation Example 11

8.84 g maleic anhydride are dissolved in 40 ml DMSO. 9.6 g2-(N-methylamino)-acetaldehyde dimethyl acetal are added drop-wise tothis solution while cooled such that the temperature does not rise anyhigher than 20° C. Subsequently, the mixture is heated to 60° C. for 30minutes.

Then 100 g Mowiol 8/88® (polyvinyl alcohol available from Hoechst havinga content of residual acetyl groups of approx. 21 wt. %) are dissolvedat 70° C. in 640 ml dimethyl sulfoxide and this solution is added to theabove mixture. The resulting mixture of the two solutions is thenstirred for 24 hours at 70° C. Subsequently, a mixture of 11.6 gbutyraldehyde and 13.6 g acetaldehyde is added drop-wise under stirringand kept at 70° C. for another 5 hours. The polymeric binder isprecipitated in an excess of water and dried for 24 hours at 40° C. in arotary drying chamber. The analytical examination of the product revealsan acid number of 29 mg KOH per gram polymer.

Preparation Example 12 based on PCT WO 93/03068

A mixture of 25 g Mowiol 5/88® (polyvinyl alcohol available from Hoechsthaving a content of residual acetyl groups of approx. 21 wt. %), 75 mlwater and 150 ml n-propanol is stirred at 70° C. for 20 hours. Thesolution is cooled to 60° C. Upon addition of 3.4 g concentratedhydrochloric acid, first a mixture of 5.4 g benzaldehyde, 7.4 gbutyraldehyde and then 9 g phthalaldehydic acid are added over 2 hours.This mixture is stirred for 2 hours at 60° C. and soda is added in anamount to obtain a pH value of 7. By means of precipitation in water,washing the polymer with water and drying for 24 hours at 40° C., aproduct is obtained having an acid number of 20 mg KOH per gram polymer.

Preparation Example 13 based on DE 20 533 63

50 g Mowital B60T® (polyvinyl butyral available from Hoechst having acontent of 70 wt. % acetal, of 26 wt. % vinyl alcohol and of 3 wt. %acetate) are dissolved in 752 g dried 1,4-dioxane at 40° C.Subsequently, 27.2 g p-toluene sulfonyl isocyanate is added drop-wiseover 20 minutes at the same temperature. This mixture is stirred foranother 4 hours at 40° C. and then the polymer is precipitated in anexcess of water. Upon thorough washing with water, the product is suckedoff and dried for 24 hours at 40° C. in a rotary drying chamber.

Preparation Example 14 based on EP-A-0 152 819

25 g Mowital B60T® (polyvinyl butyral available from Hoechst having acontent of 70 wt. % acetal, of 26 wt. % vinyl alcohol and of 3 wt. %acetate) are dissolved in 700 ml methyl ethyl ketone at 60° C. and then,upon addition of 10 g maleic anhydride and 0.7 ml triethyl amine,refluxed for 6 hours. By means of precipitation using water, washing thepolymer with water and drying for 24 hours at 40° C., a product isobtained having an acid number of 58 mg KOH per gram polymer.

Preparation Example 15 based on GB-1 396 355

100 g poly(vinylacetate-co-crotonic acid) (Mowilith CT5® available fromHoechst) are dissolved in 1,000 ml methanol. A sodium methylate solutionof 2 g sodium and 40 ml methanol is added drop-wise to this solution.This mixture is refluxed for 30 minutes and the precipitated polymerparticles are filtered off. Upon washing using methanol, the polymer isdried.

50 g of the thus obtained copolymer of crotonic acid, vinyl alcohol andvinyl acetate are dissolved in a mixture of 150 ml water and 300 mln-propanol. Upon addition of 10.9 g concentrated hydrochloric acid, 10.8g benzaldehyde and 15 g butyraldehyde are added drop-wise and themixture is heated to 60° C. under stirring for 4 hours. It isneutralized using 5 g soda. By means of precipitation using water,washing the polymer with water and drying for 24 hours at 40° C., aproduct is obtained having an acid number of 3 mg KOH per gram polymer.

EXAMPLE 1

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Binder of Preparation Example 5                                   4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The printing layer is exposed under a silver film halftone step wedgehaving a tonal range of 0.15 to 1.95, wherein the density incrementsamount to 0.15, to give a negative model using a metal halogenide lamp(MH burner, available from W. Sack) of 300 mJ/cm².

The exposed coating is treated for 30 seconds with a developer solutioncomprising

3.4 parts by weight Rewopol NLS 28® (available from REWO)

1.8 parts by weight 2-phenoxy ethanol

1.1 parts by weight diethanol amine

1.0 parts by weight Texapon 842® (available from Henkel)

0.6 parts by weight Nekal BX Paste® (available from BASF)

0.2 parts by weight 4-toluene sulfonic acid

91.9 parts by weight water.

Then the developer solution is again rubbed over the surface for another30 seconds using a tampon and then the entire plate is rinsed withwater. After this treatment the exposed portions remain on the plate.For the assessment of its photosensitivity, the plate is blackened in awet state using a printing ink.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 4and partially covered up to step 8.

For the preparation of a lithographic plate a printing layer is appliedto the aluminum foil, as explained above, exposed, developed and afterrinsing with water the developed plate is wiped and rubbed with anaqueous solution of 0.5% phosphoric acid and 6% gum arabic. The thusprepared plate is loaded in a sheet-fed offset printing machine andunder normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

EXAMPLE 2

A coating solution is prepared from the following components:

    ______________________________________                                        5.88 g      Binder of Preparation Example 5                                   2.5  g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The printing layer is exposed, developed, blackened and printed asdescribed in Example 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 4and partially covered up to step 11.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

EXAMPLE 3

A coating solution is prepared from the following components:

    ______________________________________                                        5.43   g      Binder of Preparation Example 5                                 4      g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                            0.5    g      Victoria blue (C.I. Solvent Blue 5)                             0.07   g      phosphoric acid.                                                ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The printing layer is exposed, developed, blackened and printed asdescribed in Example 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 2and partially covered up to step 8.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

EXAMPLE 4

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Binder of Preparation Example 7                                   4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The printing layer is exposed, developed, blackened and printed asdescribed in Example 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 3and partially covered up to step 8.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

EXAMPLE 5

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Binder of Preparation Example 8                                   4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The printing layer is exposed, developed, blackened and printed asdescribed in Example 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 4and partially covered up to step 9.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

EXAMPLE 6

A coating solution is prepared from the following components:

    ______________________________________                                        5.88 g      Binder of Preparation Example 6                                   2.5  g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The printing layer is exposed, developed, blackened and printed asdescribed in Example 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The first step of the gray wedge is completelycovered and those up to step 9 are partially covered.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

EXAMPLE 7

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Binder of Preparation Example 5                                   4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of sodium silicate by means ofcommon methods and the coating is dried for 4 minutes at 90° C. Theweight of the printing layer amounts to approx. 1 g/m².

The printing layer is exposed, developed, blackened and printed asdescribed in Example 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 3and partially covered up to step 10.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

EXAMPLE 8

A coating solution is prepared from the following components:

    ______________________________________                                        1.5  g      Binder of Preparation Example 5                                   0.6  g      of a terpolymer prepared by polymerization of 476                             parts by wt. styrene, 476 parts by wt. methyl                                 methacrylate and 106 parts by wt. methacrylic acid                5.24 g      of a 80% methyl ethyl ketone solution of an                                   urethane acrylate prepared by reacting Desmodur                               N 100 ® (available from Bayer) comprising hydroxy                         ethyl acrylate and pentaerythritol triacrylate                                having a double-bond content of 0.5 double                                    bonds/100 g when all isocyanate groups are                                    completely reacted                                                1.29 g      dipentaerythritol pentaacrylate                                   0.6  g      2,4-trichloromethyl-6[(4-ethoxyethylenoxy)                                    naphthyl]-1,3,5-triazine                                          0.16 g      4,4'-N,N-diethylaminobenzophenone                                 0.2         benzophenone                                                      0.19 g      3-mercapto-1,2,4-triazol                                          0.12 g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.1  g      leuco Crystal Violet.                                             ______________________________________                                    

These components are dissolved under stirring in 100 ml of a mixturecomprising

35 parts by volume methyl glycol

25 parts by volume methanol

40 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1.85 g/m².

Then, an oxygen-impermeable layer of 1.7 g/m² dry layer weight wasapplied analogously by applying a coating of an aqueous solution of thefollowing composition:

    ______________________________________                                        50     g      polyvinylalcohol (Airvol 203 ® available from                             Airproducts; 12% residual acetyl groups)                        270    g      water.                                                          ______________________________________                                    

Drying also took place for 5 minutes at 95° C.

The plate is exposed as described in Example 1; however, the amount oflight is 10 mJ/cm². Immediately upon exposure, the plates were heated to95° C. for 1 minute in order to amplify the photo polymerization takingplace. Developing and blackening takes place as described in Example 1.

The plate's ink receptivity is good. The gray wedge is completelycovered up to step 4 and partially covered up to step 6.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

EXAMPLE 9

A coating solution is prepared from the following components:

    ______________________________________                                        5.2  g      Binder of Preparation Example 5                                   2.88 g      of a 80% methyl ethyl ketone solution of an                                   urethane acrylate prepared by reacting Desmodur                               N 100 ® (available from Bayer) comprising hydroxy                         ethyl acrylate and pentaerythritol triacrylate                                having a double-bond content of 0.5 double                                    bonds/100 g when all isocyanate groups are                                    completely reacted                                                1.42 g      dipentaerythritol pentaacrylate                                   0.165                                                                              g      2-(4-methoxy-naphth-1-yl)-4,6-bis-(trichloro-                                 methyl)-s-triazine                                                0.33 g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              0.165                                                                              g      Victoria blue (C.I. Solvent Blue 5)                               0.12 g      4-phenyl-azo-diphenylamine                                        0.05 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

Then oxygen-impermeable layer of 0.3 g/m² dry layer weight was appliedanalogously by applying a coating of an aqueous solution of thefollowing composition:

    ______________________________________                                        50     g      polyvinylalcohol (Airvol 203 ® available from                             Airproducts; 12% residual acetyl groups)                        270    g      water.                                                          ______________________________________                                    

Drying Also took place for 5 minutes at 95° C.

The is exposed, developed, blackened and printed as described in Example1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The first step of the gray wedge is completelycovered and those up to step 11 are partially covered.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

EXAMPLE 10

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Binder of Preparation Example 9                                   4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed, blackened and printed as described inExample 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 3and partially covered up to step 9.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

EXAMPLE 11

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Binder of Preparation Example 10                                  4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed, blackened and printed as described inExample 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 3and partially covered up to step 9.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

EXAMPLE 12

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Binder of Preparation Example 11                                  4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed, blackened and printed as described inExample 1.

The plate's ink receptivity is good and exposed microscopic lines arevery well reproduced. The gray wedge is completely covered up to step 3and partially covered up to step 9.

The thus prepared plate is loaded in a sheet-fed offset printing machineand under normal printing conditions provides 200,000 copies of goodquality. The plate could be used for more prints.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitno change in their printing behavior in comparison to the plates thatwere not artificially aged.

Comparative Example 1

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Polyvinyl butyral having an average molecular                                 weight of 30,000 containing 70 wt. % butyral units,                           27 wt. % vinyl alcohol units and 3 wt. % vinyl                                acetate units                                                     4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed and blackened as described in Example 1.

The thus prepared plates prove to be very hard to develop. Unexposedareas can only be freed from coating residues clinging to them by meansof strong mechanic support. The unexposed portions of the coating arepartially insoluble in the developer and tend to form deposits on theplate and in the machines used in the developing process. The resolutionis poor since the spaces between fine details are not developedproperly.

Comparative Example 2

A coating solution is prepared from the following components:

    ______________________________________                                        4.38 g      Binder of Preparation Example 4                                   4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed and blackened as described in Example 1.

The reproduction of fine halftone dots is sufficient. The first step ofthe gray wedge is completely covered and those up to step 7 arepartially covered.

In comparison, the polymers prepared according to the invention exhibita higher sensitivity.

To simulate aging of the plates, they are stored for 10 days at atemperature of 40° C. and 80% relative humidity. The thus treated platesare used for printing in a sheet-fed offset printing machine and exhibitenormous wear of the solids as early as after 50,000 copies under normalconditions.

Comparative Example 3

A coating solution is prepared from the following components:

    ______________________________________                                        5.43   g      Binder of Preparation Example 12                                4      g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                            0.5    g      Victoria blue (C.I. Solvent Blue 5)                             0.07   g      phosphoric acid.                                                ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed and blackened as described in Example 1.

The gray wedge is completely covered up to step 2 and partially coveredup to step 7. In comparison, the polymers prepared according to theinvention exhibit a higher sensitivity.

Furthermore, the plate required at least 15 seconds developing time incomparison to 5 seconds in case of the printing molds of this invention.In fast developing machines and developers close to exhaustion, thisleads to plates that are not properly developed.

Comparative Example 4

A coating solution is prepared from the following components:

    ______________________________________                                        6.38 g      Polymer of Preparation Example 13                                 2    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1.5  g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.07 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed and blackened as described in Example 1.

The ink receptivity is not as good as that of the lithographic platesprepared according to the invention. The gray wedge is completelycovered up to step 2 and partially covered up to step 8.

The thus prepared plate is loaded in a sheet-fed offset printing machineand after 100,000 copies under normal printing conditions exhibits anenormous loss of micro-elements and beginning wear of the solids.

Comparative Example 5

A coating solution is prepared from the following components:

    ______________________________________                                        5.85 g      Polymer of Preparation Example 14 (based on EP-A-0                            152 819)                                                          3    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              1    g      Renol blue B2G-HW ® (copper phthalocyanine pigment                        dispersed in polyvinyl butyral available from HOECHST)            0.05 g      4-phenyl-azo-diphenylamine                                        0.1  g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed, blackened and printed as described inExample 1.

The reproduction of fine halftone dots is sufficient. The first step ofthe gray wedge is completely covered and those up to step 7 arepartially covered.

In comparison, the polymers prepared according to the invention exhibita higher sensitivity.

Comparative Example 6

A coating solution is prepared from the following components:

    ______________________________________                                        5.45 g      Scripset 540 ® (butyl semi-ester of the maleic acid                       anhydride/styrene copolymer available from Monsanto)              4    g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                              0.5  g      Victoria blue (C.I. Solvent Blue 5)                               0.05 g      phosphoric acid.                                                  ______________________________________                                    

These components are dissolved under stirring in 100 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed, blackened and printed as described inExample 1.

The ink receptivity during manual blackening of the plate isinsufficient and exposed microscopic lines are poorly reproduced. Thefirst step of the gray wedge is completely covered and those up to step7 are partially covered.

The thus prepared plate is loaded in a sheet-fed offset printingmachine. During printing the plate's ink receptivity is poor, inparticular the ink receptivity of the solids being spotted. After100,000 copies considerable wear in the solids as well as in thehalftone dots becomes apparent.

The results show that the ink receptivity of and the consistency in thenumber of prints produced by lithographic plates containing binders ofthis invention is significantly superior.

Comparative Example 7

A coating solution is prepared from the following components:

    ______________________________________                                        5.45   g      CAP ® (cellulose-acetate/phthalate available from                         Eastman Kodak)                                                  4      g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                            0.5    g      Victoria blue (C.I. Solvent Blue 5)                             0.05   g      phosphoric acid.                                                ______________________________________                                    

These components are dissolved under stirring in 100 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed, blackened and printed as described inExample 1.

The ink receptivity during manual blackening of the plate and thesensitivity are insufficient (first step of the gray wedge is completelycovered and those up to step 5 are partially covered).

The thus prepared plate is loaded in a sheet-fed offset printingmachine. During printing the plate's ink receptivity is poor, inparticular the ink receptivity of the solids being spotted. After 60,000copies considerable wear in the solids as well as in the halftone dotsbecomes apparent.

The results show that the ink receptivity and photosensitivity of andthe consistency in the number of prints produced by lithographic platescontaining binders of this invention is significantly superior.

Comparative Example 8

A coating solution is prepared from the following components:

    ______________________________________                                        6.43   g      Binder of Preparation Example 15                                3      g      polycondensation product from 1 mole 3-methoxy                                diphenylamine-4-diazonium sulfate and 1 mole 4,4'-                            bis-methoxymethyldiphenyl ether precipitated as                               mesitylene sulfonate                                            0.5    g      Victoria blue (C.I. Solvent Blue 5)                             0.07   g      phosphoric acid.                                                ______________________________________                                    

These components are dissolved under stirring in 200 ml of a mixturecomprising

30 parts by volume methyl glycol

45 parts by volume methanol

25 parts by volume methyl ethyl ketone.

After filtering the solution, it is applied to an electrochemicallyroughened and anodized aluminum foil that was subjected to anaftertreatment using an aqueous solution of polyvinyl phosphonic acid bymeans of common methods and the coating is dried for 4 minutes at 90° C.The weight of the printing layer amounts to approx. 1 g/m².

The plate is exposed, developed and blackened as described in Example 1.

The first two steps of the gray wedge are completely covered and thoseup to step 7 are partially covered. In comparison, the polymers preparedaccording to this invention exhibit a higher sensitivity. Besides, thegray wedge before blackening is 3 steps shorter, i.e. the sensitivityappears higher than it is due to minimal remaining coating residues. Incomparison to plates prepared according to this invention, thereproduction of micro-elements is poor, a fact which shows in too fewopen dark portions of blackened plates.

Furthermore, the plate requires at least 20 seconds developing time incomparison to 5 seconds in case of the printing molds of this invention.In fast developing machines and developers close to exhaustion, thisleads to plates that are not properly developed.

We claim:
 1. A polymer binder containing the units A, B, C, D and E,wherein A is present in an amount of 10 to 60 mole % and is of theformula ##STR13## B is present in an amount of 1 to 30 mole % and is ofthe formula ##STR14## C is present in an amount of 5 to 60 mole % and isof the formula ##STR15## D is present in an amount of 0 to 60 mole % andis of the formula ##STR16## and E is present in an amount of 1 to 40mole % and is of the formula ##STR17## wherein X is an aliphatic,aromatic or araliphatic spacer group,R¹ is hydrogen or an aliphatic,aromatic or araliphatic group, R², R³ and R⁴ are hydrogen or alkylgroups with carbon numbers of from 1 to 18 and Y is a saturated orunsaturated chain- or ring-shaped spacer group.
 2. The binder of claim 1containing one of the following spacer groups Y:--CR⁵ R⁶ --CR⁷ R⁸ --,--CR⁵ ═CR⁶ --, ##STR18## wherein R⁵, R⁶, R⁷, R⁸ each are independentlyhydrogen or alkyl.
 3. The binder of claim 1, wherein R¹ is hydrogen oralkyl and the spacer group X is a --CH₂, --CH(CH₃) or --CH₂ CH₂ CH₂group.
 4. The binder of claim 1, wherein R² is CH₃ and R³ and R⁴ arealiphatic groups with carbon numbers of from 1 to 6.